Autothermal reformer-reforming exchanger arrangement for hydrogen production

ABSTRACT

Low-energy, low-capital hydrogen production is disclosed. A reforming exchanger  14  is placed in parallel with an autothermal reformer (ATR)  10  to which are supplied a preheated steam-hydrocarbon mixture. An air-steam mixture is supplied to the burner/mixer of the ATR  10  to obtain a syngas effluent at 650°-1050° C. The effluent from the ATR is used to heat the reforming exchanger, and combined reformer effluent is shift converted and separated into a mixed gas stream and a hydrogen-rich product stream. High capital cost equipment such as steam-methane reformer and air separation plant are not required.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent application Ser. No. 10/708,583, filed on Mar. 12, 2004, which will issue as U.S. Pat. No. 7,220,505, on May 22, 2007, which claims benefit of U.S. Provisional Application No. 60/320,015, filed on Mar. 18, 2003. Both of which are incorporated by reference herein.

BACKGROUND

1. Field

The present embodiments relate to the production of a synthesis gas (syngas) using an autothermal reactor (ATR) and a reforming exchanger.

2. Description of the Related Art

Reforming hydrocarbons is a standard process applying a plurality of generally endothermic reactions for the production of hydrogen-containing synthesis gas used for manufacturing ammonia or methanol, for example. A conventional autothermal reforming reactor (ATR) is a form of steam reformer including a catalytic gas generator bed with a specially designed burner/mixer to which preheated hydrocarbon gas, air or oxygen, and steam are supplied. Partial combustion of the hydrocarbon in the burner supplies heat necessary for the reforming reactions that occur in the catalyst bed below the burner to form a mixture of mostly steam, hydrogen, carbon monoxide (CO), carbon dioxide (CO₂), and the like. Effluent from the steam reformer is then usually further converted in shift converters wherein CO and steam react to form additional hydrogen and CO₂, especially for ammonia or other syntheses where hydrogen is a main desired syngas constituent.

Advantages of ATR are low capital cost and easy operation compared to a conventional catalytic steam reformer, for example. Disadvantages of commercial ATR processes are the capital costs, operating difficulties, and plot area requirements associated with the air separation unit (ASU), especially where operating personnel and plot area are limited or other factors make an ASU undesirable. Where the synthesis gas is used for ammonia production, low temperature distillation has been used to remove excess nitrogen and other impurities to obtain a 99.9% purity level.

Reforming exchangers used with autothermal reformers are known, for example, from U.S. Pat. Nos. 5,011,625, and 5,122,299, to LeBlanc and U.S. Pat. No. 5,362,454 to Cizmer et al., all of which are hereby incorporated herein by reference in their entirety. These reforming exchangers are available commercially under the trade designation KRES or Kellogg, Brown and Root (KBR) Reforming Exchanger System.

A need exists for producing hydrogen from an ATR without using an ASU and/or low temperature distillation, by operating the ATR with excess air, supplying the ATR process effluent to a reforming exchanger to provide heat for additional syngas production, and partially purifying the product hydrogen stream without the need for low temperature processing for nitrogen rejection.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the present embodiments can be understood in detail, a more particular description of the present embodiments, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawing. It is to be noted, however, that the appended drawing illustrates only typical embodiments and is therefore not to be considered limiting of its scope, for the descirbed embodiments may admit to other equally effective embodiments.

The FIGURE depicts a simplified schematic process flow diagram of the ATR-reforming exchanger process according to one embodiment.

DETAILED DESCRIPTION

A detailed description will now be provided. Each of the appended claims defines a separate embodiment, which for infringement purposes is recognized as including equivalents to the various elements or limitations specified in the claims. Depending on the context, all references below to the “invention” may in some cases refer to certain specific embodiments only. In other cases it will be recognized that references to the “invention” will refer to subject matter recited in one or more, but not necessarily all, of the claims. Each of the present embodiments will now be described in greater detail below, including specific embodiments, versions and examples, but the inventions are not limited to these embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the inventions, when the information in this patent is combined with available information and technology.

Embodiments described use a reforming exchanger in parallel with an autothermal reactor (ATR) in a new hydrogen plant with reduced capital costs, reduced energy requirements, greater ease of operation, and reduced NOx and CO2 emissions, or in an existing hydrogen plant where the hydrogen capacity can be increased by as much as 40-60 percent with reduced export of steam from the hydrogen plant. The resulting process has very low energy consumption.

Embodiments described also provide a process for producing hydrogen. The process includes: (a) catalytically reforming a first hydrocarbon portion with steam and air in an autothermal reactor to produce a first syngas effluent at a temperature from 650° to 1050° C., desirably 650° to 1000° C.; (b) supplying the first syngas effluent to a reforming exchanger; (c) passing a second hydrocarbon portion with steam through a catalyst zone in the reforming exchanger to form a second syngas effluent; (d) discharging the second syngas effluent from the catalyst zone adjacent the inlet to form a syngas admixture with the first syngas effluent; (e) passing the admixture across the catalyst zone in indirect heat exchange therewith to cool the admixture and heat the catalyst zone; (f) collecting the cooled admixture from an outlet of the reforming exchanger; (g) shift converting the admixture to obtain a carbon dioxide-rich gas stream lean in carbon monoxide; and (h) separating the carbon-dioxide-rich gas stream to form a hydrogen-lean, mixed gas stream comprising nitrogen and carbon dioxide and a hydrogen-rich product stream.

If desired, the reforming, shift conversion and mixed gas separation can be at a process pressure from 10 to 200 bars, e.g. above 30 bars. The nitrogen and carbon dioxide removal can consist of membrane separation or pressure swing adsorption, or a like unit operation that can simultaneously remove a mixture of gases from the hydrogen at the process pressure and desirably does not require separate sequential steps for carbon dioxide and nitrogen removal. The process desirably includes compressing air to the catalytic reforming with a gas turbine drive and recovering heat from exhaust from the gas turbine. The catalyst zone can include catalyst tubes, and the process can further include: supplying the first syngas effluent to a shell-side of the reformer; supplying the second hydrocarbon portion with steam through the catalyst tubes; and discharging the second syngas effluent from the catalyst tubes adjacent the shell-side inlet to form the syngas admixture. The autothermal reformer can be operated with excess air. The hydrogen-rich gas stream from the shift conversion can have a molar ratio of hydrogen to nitrogen less than 3. The nitrogen and carbon dioxide removal is desirably free of cryogenic distillation, and the process is desirably free of air separation. The proportion of the first hydrocarbon portion relative to a total of the first and second hydrocarbon portions is desirably from 55 to 85 percent. The proportion of the first hydrocarbon portion relative to a total of the first and second hydrocarbon portions is more desireably 60 to 80 percent. The hydrogen product stream can have a purity of at least 70% up to 99.5%, desirably at least 90%, more desirably at least 95%, even more desirably at least 97%, and especially at least 98.5%, by volume. The process can include supplying the hydrogen product stream to a fuel cell for the generation of an electrical current, or to a hydrotreater, e.g. to upgrade a crude oil, or to other refinery processes.

In another embodiment, an apparatus for preparing syngas is provided. The apparatus includes: (a) autothermal reactor means for catalytically reforming a first hydrocarbon portion with steam and air to produce a first syngas effluent at a temperature from 650° to 1050° C.; (b) means for supplying the first syngas effluent to an inlet of a reforming exchanger; (c) means for passing a second hydrocarbon portion with steam through a catalyst zone in the reforming exchanger to form a second syngas effluent; (d) means for discharging the second syngas effluent from the catalyst zone adjacent the inlet to form a syngas admixture with the first syngas effluent; (e) means for passing the admixture across the catalyst zone in indirect heat exchange therewith to cool the admixture and heat the catalyst zone; (f) means for collecting the cooled admixture from an outlet from the reforming exchanger; (g) means for shift converting the admixture to obtain a carbon dioxide-rich gas stream lean in carbon monoxide; and (h) means for separating the carbon-dioxide-rich gas stream to form a hydrogen-lean, mixed gas stream comprising nitrogen and carbon dioxide and a hydrogen-rich product stream. The separation means of the apparatus can include a pressure swing adsorption unit or a membrane separator

One embodiment of a process according to the present invention has the general configuration shown in the FIGURE. Desulfurized natural gas or other hydrocarbon supplied from line 2 is mixed with process steam from line 4 and the mixture is preheated in a feed preheat exchanger 6. The steam to carbon ratio of the mixture is desirably from 2.0 to 4.0, e.g. about 3. A first portion of the preheated steam-hydrocarbon mixture is fed via line 8 to the burner in autothermal reformer (ATR) 10, and a second portion is supplied via line 12 to the tube-side inlet of reforming exchanger 14. If desired, additional steam can be added via line 36 to line 8.

Air is supplied via line 16 and mixed with steam from line 18, and the steam-air mixture is preheated in preheater 38, e.g. to a temperature from 200° C. to 650° C., and sent to the burner via line 20, taking due care to maintain the flame temperature in the burner below 1500° C. The air is desirably excess air, by which is meant that the resulting molar ratio of hydrogen to nitrogen (following shift conversion) in the syngas is less than about 3 (the typical stoichiometric ratio for ammonia syngas make-up). Using air instead of oxygen or oxygen-enriched air can be economically beneficial where the nitrogen content and/or hydrogen purity of the syngas is not critical, for example, in fuel cells, in the hydrotreatment of crude oil or heavy fractions thereof, or in applications where the nitrogen is inert and the presence thereof does not significantly affect the economics of the method for the use of the syngas. Air can be used as a substitute for pure oxygen when economic or space consideration restrict the use of a conventional air separation unit (ASU), such as when an ATR/reforming exchanger is used for producing hydrogen for use on a floating production storage and offtake (FPSO) facility. If desired, the air can be supplied by a compressor that driven by a gas turbine, and heat recovered from the gas turbine exhaust, for example, to preheat process feed streams, generate process steam, or the like.

The molar ratio of steam to molecular oxygen in the air-steam mixture is desirably from about 0.8 to about 1.8, more desirably about 1 to about 1.6, and the molar ratio of oxygen to carbon in the hydrocarbon feed to the ATR can be from about 0.5 to about 0.8, desirably from about 0.6 to 0.7. The split of the hydrocarbon feed to the ATR 10 (line 8) relative to the total hydrocarbon feed to the ATR 10 and the reforming exchanger 14 (line 2), is desirably from 55 to 85 percent, more desirably from 60 to 80 percent, and particularly 65 to 75 percent to the ATR. The operating conditions and flow rates are generally optimized for maximum hydrogen production.

The syngas effluent in line 22 from the ATR 10 can be supplied to the shell-side inlet of the reforming exchanger 14. The reformed gas from the outlet ends of the catalyst tubes 24 mixes with the ATR effluent and the mixture passes across the outside of the catalyst tubes 24 to the shell-side outlet where it is collected in line 26. The combined syngas in line 26 is cooled in the cross exchanger 6 and waste heat boiler 28 to produce steam for export, and supplied to downstream processing that can include a shift section 30 (which can include high temperature, medium temperature and/or low temperature shift converters), heat recovery 32, mixed gas separation 34 such as CO₂ removal (pressure swing adsorption (PSA) or membrane separation, for example), and the like, all unit operations of which are well known to those skilled in the art. The separation 34 is desirably free of low temperature or cryogenic separation processes used to remove excess nitrogen in ammonia syngas production, which require a separate upstream removal system for carbon dioxide that can solidify at the low temperature needed for nitrogen removal.

The heat requirement for the reforming exchanger 14 is met by the quantity and temperature of the ATR effluent. Generally, the more feed to the reforming exchanger, the more heat required to be supplied from the ATR effluent. The temperature of the ATR effluent in line 22 should be from 650° to 1000° C. or 1050° C., and can desirably be as hot as the materials of construction of the reforming exchanger 18 will allow. If the temperature is too low, insufficient reforming will occur in the reforming exchanger 14, whereas if the temperature is too high the metallurgical considerations become problematic. Care should also be taken to ensure that operating conditions are selected to minimize metal dusting. Operating pressure is desirably from 10 to 200 bars or more, especially at least 25 or 30 bars, and can be conveniently selected to supply the hydrogen product stream at the desired pressure, thereby avoiding the need for a hydrogen compressor.

The present invention is illustrated by way of an example. A reforming exchanger installed with an ATR as in the FIGURE where air is used in place of oxygen for 50 MMSCFD hydrogen production has a total absorbed duty in the fired process heater of 38.94 Gcal/hr, and has the associated parameters shown in Table 1 below: TABLE 1 ATR-Reforming Exchanger Process with Excess Air Catalyst Shell- Air- tube ATR ATR side steam to inlet, feed, effluent, outlet, ATR, Stream ID: line 12 line 8 line 22 line 26 line 20 Dry Mole Fraction H2 0.0200 0.0200 0.3578 0.4492 N2 0.0190 0.0190 0.4628 0.3561 0.7804 CH4 0.9118 0.9118 0.0013 0.0036 AR 0.0000 0.0000 0.0055 0.0042 0.9400 CO 0.0000 0.0000 0.0835 0.1026 CO2 0.0000 0.0000 0.0891 0.0843 0.0300 O2 0.0000 0.0000 0.0000 0.0000 0.2099 C2H6 0.0490 0.0490 0.0000 0.0000 C3H8 0.0002 0.0002 0.0000 0.0000 Total Flow KMOL/HR (dry) 312.6 713.9 4154.2 5414.7 2446.2 H₂O KMOL/HR 947.7 2164.0 2827.0 3380.6 728.9 Total Flow KMOL/HR 1260.3 2878.0 6981.2 8795.3 3175.1 Total Flow KG/HR 22288 50896 134887 156700 83990 Pressure (kg/cm² abs) 25.9 25.9 22.4 22.1 24.0 Temperature (° C.) 601 601 1011 747 621

In addition, the data in Table 1 are for an example that represents low capital cost, low energy consumption, easy operation, and reduced NO_(x) and CO₂ (56 percent less than a comparable steam reforming hydrogen plant of the same capacity) and CO₂ emissions. This process is an attractive option for construction of new hydrogen production facilities where excess nitrogen is desired or can be tolerated, or can be economically removed from the sythesis gas.

As another example, a reforming exchanger is installed with an ATR as shown in the FIGURE wherein air is used as the oxygen source, for a 50 MMSCFD hydrogen production. Typical pressures and temperatures are indicated in the FIGURE for this example, and other associated parameters are shown in Table 2 below: TABLE 2 ATR-Reforming Exchanger Process with Excess Air Oxidant ATR Shell-side Catalyst tube ATR feed effluent, line outlet, line Air-steam to Stream ID: inlet 12 line 8 22 26 ATR, line 20 Dry Mole Fraction H2 0.0200 0.0200 0.4115 0.4792 N2 0.0023 0.0023 0.4020 0.3089 0.7804 CH4 0.9612 0.9612 0.0026 0.0227 AR 0.0000 0.0000 0.0048 0.0037 0.0094 CO 0.0000 0.0000 0.0803 0.0875 CO2 0.0150 0.0150 0.0987 0.0980 0.0003 O2 0.0000 0.0000 0.0000 0.0000 0.2099 C2H6 0.0013 0.0013 0.0000 0.0000 C3H8 0.0002 0.0002 0.0000 0.0000 Total Flow 371.5 754.3 4069.7 5299.5 2094.1 KMOL/HR (dry) H2O KMOL/HR 1074.8 2182.2 2610.9 3325.1 656.2 Total Flow 1446.3 2936.5 6680.5 8624.6 2750.3 KMOL/HR Total Flow 25395 51557 124039 149434 72482 KG/HR Pressure (kg/cm2 25.5 23.6 22.8 22.5 23.6 abs) Temperature 601 601 884 659 621 (° C.)

The data in Table 2 are also for an example that represents low capital cost, low energy consumption, easy operation, and reduced NO_(x) and CO₂ emissions. The effluent recovered from the reforming exchanger includes 47.9% H₂, 30.9% N₂, 8.8% CO, and 9.9% CO₂. The reforming exchanger effluent undergoes shift conversion, as shown in the FIGURE, resulting in an effluent having a composition of 51.9% H2, 28.6% N2, 0.5% CO, and 16.6% CO2. Purification by PSA results in a purified product having a composition of 98.0% H₂, 0.80% N₂, and 1.0% CH₄.

The foregoing description of the invention is illustrative and explanatory of the present invention. Various changes in the materials, apparatus, and process employed will occur to those skilled in the art. It is intended that all such variations within the scope and spirit of the appended claims be embraced thereby. 

1) A process for reforming a hydrocarbon, comprising: catalytically reforming a first portion of a hydrocarbon feed in the presence of steam and excess air in a first catalyst zone to produce a first effluent; thermally reforming a second portion of the hydrocarbon feed in the presence of steam in a second catalyst zone to form a second effluent; combining the first effluent and second effluent to form a mixed effluent; indirectly exchanging heat from the mixed effluent to the second catalyst zone; and shift converting the mixed effluent to obtain a carbon dioxide-rich gas. 2) The process of claim 1, further comprising separating the carbon dioxide-rich gas to provide a hydrogen-lean, mixed gas, and a hydrogen rich gas, wherein the hydrogen-lean mixed gas comprises nitrogen and carbon dioxide. 3) The process of claim 1, wherein the first effluent comprises at least 35 mole percent, dry basis, hydrogen; and the second effluent comprises at least 70 mole percent, dry basis, hydrogen. 4) The process of claim 1, wherein the second catalyst zone comprises a plurality of tubes each containing a catalyst. 5) The process of claim 1, wherein thermally reforming the second portion of the hydrocarbon feed comprises passing the second portion of the hydrocarbon feed across or through the second catalyst zone, wherein the second catalyst zone is contained within a plurality of tubes. 6) The process of claim 1, wherein thermally reforming the second portion of the hydrocarbon feed comprises passing the second portion of the hydrocarbon feed across or through the second catalyst zone, wherein the second catalyst zone is disposed about a plurality of tubes. 7) The process of claim 1 wherein carbon dioxide-rich gas from the shift conversion comprises a molar ratio of hydrogen to nitrogen less than
 3. 8) The process of claim 1 wherein the first portion of the hydrocarbon feed is about 55 to about 85 percent of the total hydrocarbon feed. 9) The process of claim 1 wherein the first portion of the hydrocarbon feed is about 60 to about 80 percent of the total hydrocarbon feed. 10) A process for generating an electrical current comprising the process of claim 1 and supplying the hydrogen-rich product gas to a fuel cell. 11) A hydrotreating process comprising the process of claim 1 and supplying the hydrogen-rich product gas to a hydrotreater. 12) A system for reforming a hydrocarbon, comprising: a first reactor comprising a burner section and a catalyst zone disposed beneath the burner section; a second reactor comprising a plurality of tubes disposed therein, wherein a catalyst for reforming an hydrocarbon is located either in the tubes or outside the tubes; and a shift converter. 13) The system of claim 12, further comprising a mixed gas separation unit. 14) The system of claim 12, wherein the shift converter operates at high temperature, medium temperature, low temperature, or any combination thereof. 15) The system of claim 13, wherein the mixed gas separation unit comprises a pressure swing adsorption unit. 16) A system for reforming a hydrocarbon, comprising: means for catalytically reforming a first portion of a hydrocarbon feed in the presence of steam and excess air in a first catalyst zone to produce a first effluent; means for thermally reforming a second portion of the hydrocarbon feed in the presence of steam in a second catalyst zone to form a second effluent, wherein the first effluent and second effluent are combined to provide a mixed effluent; means for indirectly exchanging heat from the mixed effluent to the second catalyst zone; and means for shift converting the mixed effluent to obtain a carbon dioxide-rich gas. 17) The system of claim 16, further comprising: means for separating the carbon dioxide-rich gas to provide a hydrogen-lean, mixed gas, and a hydrogen rich gas, wherein the hydrogen-lean mixed gas comprises nitrogen and carbon dioxide. 18) A process for reforming a hydrocarbon, comprising: catalytically reforming a first portion of a hydrocarbon feed in the presence of steam and excess air in a first catalyst zone to produce a first effluent; thermally reforming a second portion of the hydrocarbon feed in the presence of steam in a second catalyst zone to form a second effluent; combining the first effluent and second effluent to form a mixed effluent; indirectly exchanging heat from the mixed effluent to the second catalyst zone; shift converting the mixed effluent to obtain a carbon dioxide-rich gas; separating the carbon dioxide-rich gas to provide a hydrogen-lean, mixed gas and a hydrogen rich gas, wherein the hydrogen-lean mixed gas comprises nitrogen and carbon dioxide; and hydrotreating a hydrocarbon using the hydrogen rich gas. 19) The process of claim 18, wherein the first effluent comprises at least 35 mole percent, dry basis, hydrogen; and the second effluent comprises at least 70 mole percent, dry basis, hydrogen. 20) The process of claim 18, wherein the second catalyst zone comprises a plurality of tubes each containing a catalyst. 21) The process of claim 18, wherein thermally reforming the second portion of the hydrocarbon feed comprises passing the second portion of the hydrocarbon feed across or through the second catalyst zone, wherein the second catalyst zone is contained within a plurality of tubes. 22) The process of claim 18, wherein thermally reforming the second portion of the hydrocarbon feed comprises passing the second portion of the hydrocarbon feed across or through the second catalyst zone, wherein the second catalyst zone is disposed about a plurality of tubes. 23) The process of claim 18, wherein the first portion of the hydrocarbon feed is about 55 to about 85 percent of the total hydrocarbon feed. 24) The process of claim 18, further comprising supplying compressed air from a gas turbine to the first catalyst zone, and recovering heat from an exhaust gas from the turbine. 25) The process of claim 1, further comprising supplying compressed air from a gas turbine to the first catalyst zone, and recovering heat from an exhaust gas from the turbine. 